Process of and apparatus for the production of coarse crystals by evaporation in vacuo and intermittent cooling



March 1 1936- 1 ,w. GENSECKE' ,6 5

' PROCESS OF AND APPARATUS FOR THE PRODUCTION OF OOARSE CRYSTALS 1 BY EVAPORATION IN VACUO AND INTERMITTENT COOLING v Filed-Nov. 29, 19:2 '3 Sheets-Sheet- 1 March 17, 1936. C w E E 2,034,615

PROCESS OF AND APPARATUS FOR THE PRODUCTION OF COARSE CRYSTALS BY EVAPORATION IN' VACUQ AND INTERIIITTBNT COOLING Filed Nov. 29, 1952 3 Sheets-Sheet 2 Pressure akfmm-e in mm. waryazgq 5' 1o 1 60 I wadsamfiemmre 5 .4.

March 17, 1936. w GENSECKE "2,034,615

PROCESS OF AND APPARATUS FOR THE PRODUCTION OF COARSE CRYSTALS BY EVAPORATION IN VACUO AND INTERMITTBNT- COOLING Filed Nov. 29, 1952- 3'Shee'ts-Shejefi s PROCESS OF APPARATUS FOR THE PRODUCTION OF COARSE CRYSTALS BY EVAPORATION nu VACUO a TENT coonmc l INTERNET- elm coke, Gonzenheim, m rmon-the-Main, Gel Til; r Lurgi Corporation, New

tion oi New York assignor to American York, N. Y., a corpora- Application November 29, 1932, Serial No. 644,922 in Ge November 30, 1931 a oi. (oi. 23 l) This invention relates to a process of and apparatus for the production of coarse crystals by evaporation in vacuo with intermittent cooling. If, at a given temperature, the solution of a salt which becomes less soluble as the temperature falls, is in estate of saturation, the cooling of such solution is not immediately accompanied by deposition of crystals. The spontaneous deposition oi crystals from the solution does not begin unth the cooling has passed through a certain range of, temperature, i. e. the zone of metastable saturation. In many cases, the crystals eventually deposited are of very fine grain. Crystals can be deposited from solutions that are in a state of metastable saturation, by introducing into the solution crystals of the same or another salt.

The present invention relates to the cultivation of coarse crystals from such saline solutions 0 in which the temperature zone ofmetastable saturation has a range of only a few degrees centigrade, *and which normally deposit finegrained crystals onbeing cooled below said zone of metastable saturation.

It is known that coarse crystals, the size of which depends on the duration of the cooling period, can be obtained by gradually cooling saturated solutions of salts oi this kind in vessels equipped with cooled stirring mechanism. According to the literature, it is essential that the solution depositing the crystals should remain within the range of the zone of metastable satoration throughout the cooling process. Even during the crystallization of salts from solutions in a condition of metastable saturation, it is possible for a portion of the salt to deposit in a flne-grainedcondition. If, however, the cooling proceeds very slowly during the condition of metastable saturation, at coarse-grained salt is obtained, provided, of course, a sumcient number of crystals be maintained in suspension in the solution-a condition that can be fulfilled by stirring, or by keeping the entire cooling apparatus in motion.

Apparatus have also been constructed in which the contents of the cooling apparatus are passed over a cooling surface at such a high velocity that the cooling efiect, that is, the difference between the temperature at which the solution reaches the cooling surface and that at which it leaves said surface, is less than 1 C, This slightly supercooled solution is brought into contact with nuclear crystals, by which means the amount of salt corresponding to the degree of supersaturation is depositedin accuse-grained form.

The known methods for producing coarse crystals consist, therefore, in cooling at a very slow rate, or elseln thecase of instantaneous coolingin lowering the temperature to only a very slight extent, e. g. less than 1 C. Such methods are not easy to operate, since undesirable deposits of salts readily occur in the event of this maximum permissible temperature diiference being exceeded. In treating large quantitles of saline solutions, for example in the potash industry, endeavours have long been made to recover, for further use in the process, the heat of the vapours givenofi during the cooling stage. on this account, the method of indirect cooling, or cooling by gradual evaporation, for obtaining coarse crystals of the salts concerned, has been abandoned, and cooling by spontaneous evaporation in vacuo has been employed instead. For this purpose, potassium chloride solution is usually cooled from about 90 C. to 30 C. in tour or five stages so that an average temperature drop of about C. occurs in each stage. With this fall in temperature it is impossible to cultivate coarse crystals.

Vacuum cooling apparatus, consisting of an elongated pan are also known. The pen is divided into several compartments, transversely in relatlon to its axis. The partitions are provided with openings only at their lowest point, so that the solution from which the dissolved salts are to be deposited in crystalline form can flow through the several compartments in succession. There is no communication between the vapour spaces of the compartments, and the vapours are led away from each space independently. The vacuum increases, to an equal extent, in each successive compartment, in the direction of flow, so that the difference in vapour pressure between the several successive compartments is the same.

With such an adjustment of the negative pressures in the several compartments, no regular cultivation. of the crystals can be obtained if the cooling of the solutions in each stage is greater than the temperature range of the zone of metastable saturation, even when the pressure difference maintained between the several compartments is small and the compartments are provided with stirring mechanism-a practice also known in connection with other vacuum cooling plants. If it were desired to effect the vacuum cooling within the metastable zone, the number of apparatus to be connected in series would be so large that practical and economical considerations must cause such a plant to be regarded as unsuitable.

According to the present invention, the cultivation of crystals by the vacuum cooling of solutions depositing salts upon cooling-such as solutions of sodium sulphate, sodium carbonate, magnesium sulphate or potassium chloride-is carried out in such a manner that the difference between the admission and outlet temperature of the solution is admitted at such a depth below the level of the liquid that the pressure of the column of liquid above the point of entry is about equal to the pressure drop the solution sustains in that stage.

ual evaporation is ensured in all cases.

The procedure which is apparently contradictory to theory, but has been proved accurate by numerous experiments, can be explained as follows:

If a saturated solution be introduced at such a depth below the level of the liquid in a cooling apparatus that no evaporation is as yet able to occur in the supply pipe, the freshly admitted solution will begin to' evaporate at a certain depth below the level of the liquid. If, for example, the absolute vapour tension above the solution be 55 mm. mercury gauge (corresponding to a saturated-steam temperature of 40 C.) and the solution be admitted with a temperature of 45 0., the first bubble is liberated at about 230 mm. below the surface of the liquid, provided the specific gravity of the liquid above the bubble 1. However, since the solution continues to cool on its way to the evaporative surface, the column of liquid above the bubbles of vapour already forming at the deepest point is not uniform, but consists of a mixture of vapour and liquid, the speciflc gravity of which is considerably lower than that of the solution itself. Consequently, the height of this layer of vapour and liquid must be kept substantially higher than specified above for pure liquid. It must amount to 600 mm. or more, so that a vertical path of more than 600 mm. must be available between the admission point and the surface of the liquid in the cooling apparatus, in order to cool the solution down from 45 C. to 40 C. If now, nuclear crystals in sumcient number be brought into the solution, for example by slow stirring, no fine crystals of the salt will form, because the path of the freshly admitted solution from the'inlet to the surface of the liquid will be so great, and therefore the time taken by the solution to travel said path, will be so long that the crystallization occurring as cooling progresses will take place entirely on the nuclear crystals and the solution will be maintained within the zone of metastable saturation. of course, the temperature drop cannot be too greatly increased in a single stage, because, in such case, the liberation of vapour would be so intensive as to allow the freshly admitted liquid tobe carried very quickly to the surface, so that the separation of the salt would no longer take place entirely within the zone of metastable temperature, and fine-grained salt would predomi nate. By maintaining a temperature difference of 3 to 6 0., uniform ebullition occurs and the desired effect is thereby obtained. In these cir- In this manner a sufficiently grad-' cumstances the evaporative surface plays only a secondary part. On the other hand, it is necessary to maintain saline crystals in suspension throughout, by gradual motion. Moreover, there is no-need to have an excessively large volume of liquid in the apparatus, a column of liquid 1 metre in height being suiiicient, in practice, with the specified temperatures. Accordingly, conical-bottom pans, such as are used for cooling solutionsof potassium chloride and have, as is known, a height of 6 to 8 metres, can be subdivided by means of horizontal partitions, so that,

for example, three cooling stages working under different pressures, can be arranged for in each apparatus. If a 4-stage vacuum-cooling plant be modified in this manner, twelve cooling stages will be obtained instead of four, so that a temperature drop of 5 C. is present in each of the newly established stages, thus enabling crystals of any convenient size to be cultivated.

In order more clearly to disclose the nature of the present invention, reference is madeto the accompanying drawings, which illustrate diagrammatically and by way of example two embodiments of apparatus which have proved specially suitable for the process according to the invention. Figures 1 and 2 are diagrammatic vertical sections of the two embodiments of the apparatus; Fig. 3 is a section along the line AB of Fig. 2; Fig. 4 is a diagram typically explaining the temperature and vapour-pressure conditions in the process according to the invention and Fig. 5 is a diagrammatic showing of a nine stage apparatus.

In Figs. 1 and 5, l denotes a known type of cooling apparatus which, according to the invention, is divided into three stages or chambers by the horizontal partitions 2. In each of these three chambers is a certain depth of liquid The solution to be cooled is admitted through the pipe 3 into the bottom of chamber 4. In

' this chamber 4 when, for example, the temperature range of metastable saturation of the solutlon is 2 C., the solution-is cooled through 4 C.

and is then passed through the overflow pipe 5, into the chamber 6, the mouth of said pipe 5 being also as low as possible in the chamber 6. From the chamber 6, the solution finally passes through a similar pipe 1, into the chamber 8. The solution is also cooled through 4 C. in each of the chambers 6 and 8. The stirrer shaft it rotates the blades In, H and I2 and thereby maintains a certain quantity of crystals in suspension. The stirring mechanism may be of any suitable design, so that, for example, the solution in each chamber is moved by a horizontally-in stead of vertically-guided shaft (see Figs. 2 and 3). The pipes 5 and"! are preferably located outside the apparatus, in order to be more readily accessible. The vapours formed in the several stages are led away through the pipes l3, l4 and i5, either jointly into a single condenser 31 (see unit C, Fig. 5), in which the liquid required for preparing the solution to be treated is preheated, or else as also appears from Fig. 5, units A and B into separate condensers 34, 35 and 36 for each chamber 4, 6 and 8 of both units A and B. In the former case, the vapour from the chambers 4 and 5 is throttled to the pressure of that from chamber 8. In the other case, the dissolving liquid can be preheated to a greater extent, since the vapours from chambers 4 and 6 have a higher saturated-steam temperature than those from chamber 8. The solution and deposited crystals are Jointly evacuated from the chamber seasons not absolutely essential that the apparatus i should be sub-divided by means othorizontai partitions. The partitims may also be conical, chiefiy when partial deposits are formed as the result of increased separation oi the salt in cooling. In such case-the liquor would be drawn on from the conical bottom through a siphon instead of from the surface.

Figs. 2 and 3 represent a cylindrical apparatus ii, divided into three chambers 26, 2i and 22 by the partitions i 8 and i9. The solution from which the salts are to be deposited enters the chamber 29 through the supply pipe 28. It pa successively through the chambers 2i and 22 by way of openings 26 and 25 in the bottom part of the partitions i8 vand i9, and is run ofl from the.

final chamber through the overflow 263. The shaft 2?,which passes through all the chambers, carries stirrer arms 28, 29 and 8b. The outlets for the vapours from the in; w are denoted by iii, 82 and 83.

The apparatus according to Fig. 2 serve, .for example, as the 4th, 5th and 6th cooling stages in the crystal-cultivation process oi the present invention, the diagram of Fig. 4 being characteristic of the invention. According to this diagram the solution is cooled through 6 C. in each stage. The temperature of the vapour liberated from the solution prior to entering the first stage, is 90 0. Since the cooling in each stage is 6 0., the saturated-steam temperature oi the vapours in the first stage is 8d C., in the second 78 C., in the third 72 C in the fourth '66. C., in the fifth 60 0., in the sixth 54 (3., and

.to' Wand 509 mm. water reuse r p ctive yl'i ie levi'eloithe liquidineachchamberis determinedby these pressure diflerences. it iollows thereiore that, in all cases, the prescrystals in suspension therein, p

sure diiference between each. two successive chambers is er than that -between the two preceding stages. It is only; by maintaining these conditions of pressure and temperature that coarse z s can be obtained, even under the most diflic cirocea by the evaporation 02 saline solutions in vacuo.

I cl: 1. as for crystallizlng dissolved substances from solutions thereof which comprises providing and maintaining a series or bodies or the solution, maintaining a lower temperature in and a lower pressure on each succeeding oi the series, agitating each of said bodies to maintain 1:: solution through said series oi bodies of solution begin- 1 ning with the body at the highest temperature and proceeding through the series to the body tionis introduced and withdrawnsubntially twice the of temt'ure of the zone of metastable saturation or the solution.

.2. s as defined in claim 1 in which the temperature difference between-the points at which solution is introduced intoand withdrawn from each body is at least once andnot more twice the range ortemperature oi the zone of metastable saturation of the solution.

3. as as defined in claim 1 in which the I" height of each body of liquid between the points at which thesolution is introduced and with-.

drawn is sui'floient to provide a hydrostatic pressure substantially equal to the diilerence between T which solution is introduced into and withdrawn from each body is at least .8 C. and not more than 6C. 

